CN114927754A - Polymer solid electrolyte, preparation method thereof and solid battery - Google Patents
Polymer solid electrolyte, preparation method thereof and solid battery Download PDFInfo
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- CN114927754A CN114927754A CN202210737559.7A CN202210737559A CN114927754A CN 114927754 A CN114927754 A CN 114927754A CN 202210737559 A CN202210737559 A CN 202210737559A CN 114927754 A CN114927754 A CN 114927754A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 105
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 78
- 239000007787 solid Substances 0.000 title abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000000178 monomer Substances 0.000 claims abstract description 98
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000011230 binding agent Substances 0.000 claims description 36
- 239000006258 conductive agent Substances 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical group 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 9
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 7
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 7
- 229910010941 LiFSI Inorganic materials 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 description 28
- 239000005518 polymer electrolyte Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- LQEJKDNALLXRCT-UHFFFAOYSA-N chloroform;toluene Chemical compound ClC(Cl)Cl.CC1=CC=CC=C1 LQEJKDNALLXRCT-UHFFFAOYSA-N 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229910013075 LiBF Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The embodiment of the application provides a polymer solid electrolyte, a preparation method thereof and a solid battery, and relates to the field of batteries. The preparation method of the polymer solid electrolyte comprises the steps of mixing grafted silica, a monomer 1, a monomer 2 and a metal salt in an organic solvent, and catalyzing to enable the grafted silica, the monomer 1 and the monomer 2 to be polymerized. The polymer solid electrolyte prepared by the preparation method has high mechanical strength and ionic conductivity, and can be used for preparing a solid battery with high voltage, high specific energy, good temperature resistance and difficult leakage.
Description
Technical Field
The application relates to the field of batteries, in particular to a polymer solid electrolyte, a preparation method thereof and a solid battery.
Background
The traditional (lithium) battery generally contains electrolyte which can conduct ions and ensure that the battery obtains the advantages of high voltage, high specific energy and the like. However, the conventional liquid electrolyte has strong toxicity, is easy to volatilize and is inflammable, so that the safety problems of liquid leakage, fire, explosion and the like can be caused. The use of solid electrolytes instead of electrolytes to function as ion conductors has therefore appeared in the prior art.
At present, all-solid-state electrolyte solutions are generally based on PEO-lithium salt-SiO 2 /Al 2 O 3 Systems, but such solid state electricityThe conductivity of the electrolyte is low (typically less than 10) -5 S·cm -1 ) The mechanical strength of the electrolyte membrane is also poor.
Disclosure of Invention
The polymer solid electrolyte prepared by the preparation method of the embodiment of the application has high conductivity and mechanical strength, and the solid battery containing the polymer solid electrolyte has low internal resistance and large battery capacity.
In a first aspect, an embodiment of the present application provides a preparation method of a polymer solid electrolyte, in which grafted silica, a monomer 1, a monomer 2, and a metal salt are mixed in an organic solvent, and then the grafted silica, the monomer 1, and the monomer 2 are polymerized through catalysis; the structural general formula of the monomer 1 is as follows:
wherein i is any value between 0 and 500; the structural general formula of the monomer 2 is as follows:
wherein j is an arbitrary value between 0 and 10, k is an arbitrary value between 0 and 10, and a cation
Is at least one of alkali metal ions, alkaline earth metal ions and structures shown in formulas 1 to 7; wherein the formula 1:
formula 2:
formula 3:
formula 4:
formula 5:
formula 6:
formula 7:
R 1 、R 2 、R 3 、R 4 each is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In the above-mentioned technical scheme, the polymerization reaction is carried out under the condition that the mercapto group in the monomer 1 provides a polymerization site, and the double bond in the monomer 2 and the grafted silica provides a polymerization site to produce the main body portion of the final polymer electrolyte. The main body part of the grafted silica is silica, so that a rigid supporting structure is provided for the final polymer, and the polymer electrolyte has good mechanical strength. The ethylene oxide units in monomer 1 provide ion conducting units of the polymer and play a crucial role in the ionic conductivity of the polymer. The rigid ionic unit structure in the monomer 2 can reduce the crystallinity of the polymer, and plays an important role in improving the ionic conductivity and cation transference number of the polymer. The combination of the three can ensure that the mechanical strength and the ionic conductivity of the polymer solid electrolyte generated subsequently are higher, and when the polymer solid electrolyte is used for preparing the solid battery, the internal resistance of the solid battery can be reduced, the battery capacity of the solid battery can be improved, and the service life of the solid battery can be prolonged. In addition, although the metal salt is not added to participate in the above-mentioned party reaction, the metal salt can provide more freely moving ions for the polymer solid electrolyte, and further enhance the ionic conductivity of the polymer solid electrolyte. The polymer solid electrolyte prepared by the preparation method has the function of conducting free ions, and can be used for preparing a solid battery with high voltage, high specific energy, good temperature resistance and difficult leakage.
In one possible implementation, the polymerization takes place between the monomer 1, the monomer 2 using photocatalytic grafted silica.
In the technical scheme, the photocatalysis does not use a catalyst, so that the formed polymer is ensured to have no catalyst residue, and the mechanical property and the conductivity of the prepared polymer solid electrolyte are not influenced.
In one possible implementation, the metal salt is a lithium salt.
In the technical scheme, when the metal salt in the polymer solid electrolyte is a lithium salt, the lithium ion battery can be used for preparing a lithium battery with high energy density.
In one possible implementation, the lithium salt includes LiP (R) f1 R f2 R f3 R f4 R f5 R f6 )、LiB(R f1 R f2 R f3 R f4 )、LiN(SO 2 R f1 )(SO 2 R f2 )、LiC(SO 2 R f1 )(SO 2 R f2 )(SO 2 R f3 ) At least one of lithium difluoro oxalate borate, lithium bis (oxalate) borate, lithium perchlorate and lithium hexafluoroarsenate, wherein R is f1 、R f2 、R f3 、R f4 、R f5 、R f6 Are respectively C n F 2n+1 Wherein n is more than or equal to 0 and less than or equal to 10; optionally, the lithium salt is LiPF 6 、LiBF 4 And at least one of LiTFSI (lithium bistrifluoromethanesulfonylimide), LiFSI (lithium bistrifluorosulfonylimide), liddob (lithium oxalato borate), LiBOB (lithium dioxaoxalato borate), lithium perchlorate, and lithium hexafluoroarsenate.
In one possible implementation, the grafted silica is 0.5% to 50%, the monomer 1 is 0.25% to 25%, the monomer 2 is 0.25% to 25%, and the metal salt is 0% to 99% by mass.
In the above technical scheme, when the content of the metal salt is 0%, the prepared polymer solid-state battery does not contain the metal salt, and at this time, the cation in the monomer 2
Can function to provide free-moving ions.
In one possible implementation, the grafted silica is prepared by modifying silica with a silane coupling agent which is
Wherein e is an arbitrary value between 0 and 10, f is an arbitrary value between 0 and 10, g is an arbitrary value between 0 and 10, and h is an arbitrary value between 0 and 10.
In the technical scheme, the grafted silica prepared by modifying the silica with the silane coupling agent silicon can easily perform a polymerization reaction with the monomer 1 and the monomer 2 to generate a polymer.
In a second aspect, embodiments of the present application provide a polymer solid electrolyte, which is prepared by the above preparation method.
In the technical scheme, the polymer solid electrolyte prepared by the preparation method has high mechanical strength and high conductivity, and can be used for preparing a solid battery with high electric capacity and long service life.
In a third aspect, an embodiment of the present application provides a solid-state battery, which includes an aluminum current collector, a positive electrode layer, a polymer solid electrolyte layer, a negative electrode layer, and a copper current collector, which are sequentially stacked, where the polymer solid electrolyte layer is formed by the above-mentioned polymer solid electrolyte.
In the technical scheme, the polymer solid electrolyte is used as the polymer solid electrolyte layer, so that the solid battery has good battery capacity and service life, and the solid battery has good temperature resistance and safety performance.
In one possible implementation, the thickness of the copper current collector is between 10nm and 20 μm; and/or the thickness of the aluminum current collector is 10 nm-20 μm; and/or the thickness of the anode layer is 10 nm-100 mu m; and/or the thickness of the negative layer is 10 nm-100 mu m; and/or the thickness of the polymer solid electrolyte layer is 10 nm-100 mu m.
In one possible implementation, the positive electrode layer comprises a positive electrode material, a conductive agent, a binder, and a polymer solid electrolyte; optionally, by massThe content of the anode material is 50-99.8%, the content of the conductive agent is 0.1-15%, the content of the binder is 0-5%, and the content of the polymer solid electrolyte is 0.1-30%; optionally, the positive electrode material is carbon-coated LiM 1 PO 4 And/or LiM 2 O 2 Wherein the element M 1 Is one or more elements of Fe, Co, Ni and Mn, and element M 2 Is one or more of Ni, Co, Mn and Al, and the particle diameter of the anode material is 0.01-50 μm; optionally, the conductive agent is one or more of carbon black, acetylene black and carbon nanotubes, and the diameter of the conductive agent is 0.01-50 μm; optionally, the binder is one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), polytetrafluoroethylene, polyacrylate and polyacrylate, and the weight average molecular weight of the binder is 1 to 500 ten thousand.
In the technical scheme, the polymer solid electrolyte can also be used for preparing the positive electrode layer, so that the solid battery is better in temperature resistance, higher in safety performance and less prone to leakage accidents.
In one possible implementation, the negative electrode layer includes a negative electrode material, a conductive agent, a binder, a polymer solid electrolyte; optionally, the content of the negative electrode material is 50-99.8%, the content of the conductive agent is 0.1-15%, the content of the binder is 0-5%, and the content of the polymer solid electrolyte is 0.1-30% by mass; optionally, the main material of the negative electrode material is one or more of lithium powder, graphite, silicon carbon and SiOx, and the particle diameter of the negative electrode material is 0.01-50 μm; optionally, the conductive agent is one or more of carbon black, acetylene black and carbon nanotubes, and the particle diameter of the conductive agent is 0.01-50 μm; optionally, the binder is one or more of styrene butadiene rubber, polyacrylate and polyacrylate, and the weight average molecular weight of the binder is 1 to 500 ten thousand.
In the technical scheme, the polymer solid electrolyte can also be used for preparing the negative electrode layer, so that the solid battery is better in temperature resistance, higher in safety performance and less prone to leakage accidents.
In one possible implementation, the negative electrode layer may also be a lithium metal foil or a lithium copper composite foil.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic representation of the principle of formation of grafted silica in the examples of the present application;
FIG. 2 is a schematic structural view of a polymer in an example of the present application;
fig. 3 is a schematic structural view of a solid-state battery in an embodiment of the present application.
Icon: 100-an aluminum current collector; 200-a positive electrode layer; 300-a polymer solid electrolyte layer; 400-negative electrode layer; 500-copper current collector.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The polymer solid electrolyte, the method for producing the same, and the solid-state battery according to the embodiments of the present application will be specifically described below.
The embodiment of the application provides a polymer solid electrolyte, and the preparation method comprises the following specific steps:
s100, preparing grafted silicon dioxide.
In this step, the silica is generally modified to obtain grafted silica; in the subsequent preparation process, the modified grafted silicon dioxide can be easily subjected to polymerization reaction with the monomer 1 and the monomer 2.
In particular, the grafted silica is generally a silica silane coupling agentModified to obtain; by way of example, in this step, the dioxide is typically nano-sized, sonicated. Of course, in other embodiments, the silica may be treated by acid treatment, alkali treatment, doping treatment, or the like, and then modified by using a silane coupling agent; wherein the silane coupling agent is
Wherein e is an arbitrary value between 0 and 10, f is an arbitrary value between 0 and 10, g is an arbitrary value between 0 and 10, and h is an arbitrary value between 0 and 10, and the reaction principle is shown in fig. 1. In FIG. 1, the spherical groups in the resulting grafted silica represent that the grafted silica is three-dimensionally crosslinked (since the three-dimensional crosslinked structure is complicated and is difficult to represent by one structural formula, they are collectively represented by the spherical groups in FIGS. 1 and 2), and there are four or more linking groups on the spherical groups, and in the subsequent step, polymerization can be formed by means of a plurality of linking groups on the spherical groups.
S200, preparing the polymer solid electrolyte. The specific process of the step is generally as follows: mixing the monomer 1, the monomer 2, the metal salt and the grafted silicon dioxide in S100 in an organic solvent, and then catalyzing to polymerize the grafted silicon dioxide, the monomer 1 and the monomer 2 to form a polymer; wherein the structural general formula of the monomer 1 is as follows:
i is any value between 0 and 500; the structural general formula of the monomer 2 is as follows:
j is an arbitrary value between 0 and 10, k is an arbitrary value between 0 and 10, and cation
Is alkali metal ion, alkaline earth metal ion, in the structure shown in formula 1-formula 7One kind of the compound is used; wherein the formula 1:
formula 2:
formula 3:
formula 4:
formula 5:
formula 6:
formula 7:
R 1 、R 2 、R 3 、R 4 each is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The metal salt can be lithium salt, sodium salt, magnesium salt, etc.; the metal salt in this embodiment is, illustratively, a lithium salt, and the polymer solid electrolyte thus obtained can be used for the production of a lithium battery having a higher energy density than a sodium battery, a magnesium battery, or the like. The lithium salt includes LiP (R) f1 R f2 R f3 R f4 R f5 R f6 )、LiB(R f1 R f2 R f3 R f4 )、LiN(SO 2 R f1 )(SO 2 R f2 )、LiC(SO 2 R f1 )(SO 2 R f2 )(SO 2 R f3 ) At least one of lithium difluoro (oxalato) borate, lithium di (oxalato) borate, lithium perchlorate and lithium hexafluoroarsenate, wherein R is f1 、R f2 、R f3 、R f4 、R f5 、R f6 Are respectively C n F 2n+1 Wherein n is more than or equal to 0 and less than or equal to 10; alternatively, the lithium salt is LiPF 6 、LiBF 4 、LiTFSI、LiFSI、LiDFOB、LiBOB、LiClO 4 、LiAsF 6 At least one of (1).
The schematic structure of the polymer produced in this step is shown in fig. 2, and it can be seen from fig. 2 that the metal salt does not participate in the formation of the polymer, but the polymer is formed by polymerization among the monomer 1, the monomer 2 and the grafted silica. The main body part of the grafted silica is silica, so that a rigid supporting structure is provided for the final polymer, and the polymer electrolyte has good mechanical strength. The ethylene oxide units in monomer 1 provide ion conducting units of the polymer and play a crucial role in the ionic conductivity of the polymer. The rigid ionic unit structure in the monomer 2 can reduce the crystallinity of the polymer, and plays an important role in improving the ionic conductivity and cation transference number of the polymer. The combination of the three can ensure that the mechanical strength and the ionic conductivity of the polymer solid electrolyte generated subsequently are both higher. The formed solid polymer can act like a solvent and dissociate metal salts, and can conduct metal ions; the metal salt acts as a solute and provides free ions (cation Y in monomer 2) ⊕ Also can provide certain freely moving ions), the metal salt and the polymer act together, the polymer solid electrolyte can be ensured to have good mechanical strength and ionic conductivity, free ions can be conducted, and the solid battery with high voltage, high specific energy, good temperature resistance and difficult leakage can be prepared. In addition, in order to ensure that the polymer reaction can be normally carried out, in this example, the raw materials include, by mass, 0.5% to 50% of grafted silica, 0.25% to 25% of monomer 1, 0.25% to 25% of monomer 2, and 0% to 99% of metal salt. When the content of the metal salt is 0%, the polymer solid-state battery is prepared without the metal salt, and the cation Y in the monomer 2 ⊕ Can function to provide free-moving ions.
In addition, in the embodiment, the grafted silica, the monomer 1 and the monomer 2 are polymerized by using photocatalysis, so that the catalyst can be prevented from remaining in the polymer solid electrolyte, and the mechanical property and the electrochemical property of the polymer solid electrolyte cannot be influenced; of course, in other embodiments, the catalyst may be used for catalysis.
The embodiment of the present application further provides a solid-state battery, which includes an aluminum current collector 100, a positive electrode layer 200, a polymer solid electrolyte layer 300 formed by the above polymer solid electrolyte, a negative electrode layer 400, and a copper current collector 500 (see fig. 3 for a schematic structural diagram of the solid-state battery) that are sequentially stacked; illustratively, the copper/aluminum current collector 100 has a thickness of 10nm to 20 μm, the positive electrode layer 200 has a thickness of 10nm to 200 μm, the negative electrode layer 400 has a thickness of 10nm to 200 μm, and the polymer solid electrolyte layer 300 has a thickness of 10nm to 200 μm. The assembly method of the battery in the embodiment of the application is generally as follows: the prepared polymer solid electrolyte layer 300, the positive electrode layer 200 and the negative electrode layer 400 are sliced, and then the aluminum current collector 100, the positive electrode layer 200, the polymer solid electrolyte layer 300, the negative electrode layer 400 and the copper current collector 500 are assembled in a lamination manner and hot-pressed at 100 ℃.
The solid-state battery with the polymer solid-state electrolyte layer 300 has the advantages of large battery capacity, long service life, difficult leakage of electrolyte, and good temperature resistance and safety performance. In addition, the positive electrode layer 200 and the negative electrode layer 400 in this embodiment may contain the above-described polymer solid electrolyte; therefore, the temperature resistance of the solid-state battery is better, the safety performance is higher, and the leakage accident is less likely to happen.
Specifically, in this embodiment, the positive electrode layer 200 includes a positive electrode material, a conductive agent, a binder, and a polymer solid electrolyte, where the positive electrode material is 50% to 99.8%, the conductive agent is 0.1% to 15%, the binder is 0% to 5%, and the polymer solid electrolyte is 0.1% to 30%. Optionally, the positive electrode material is carbon-coated LiM 1 PO 4 (M 1 One or more elements of Fe, Co, Ni, Mn) and/or LiM 2 O 2 (M 2 One or more elements selected from Ni, Co, Mn and Al), and the particle diameter of the positive electrode material is 0.01-50 μm. Optionally, the conductive agent is one or more of carbon black, acetylene black and carbon nanotubes, the particle diameter of the conductive agent is 0.01-50 μm, and the conductive agent can also be used in the negative electrode layer 400. Optionally, the binder isThe adhesive is one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), polytetrafluoroethylene, polyacrylate and polyacrylate, and the weight average molecular weight of the adhesive is 1-500 ten thousand. The positive electrode layer 200 in this embodiment can be produced by the following method: the grafted silicon dioxide, the monomer 1, the monomer 2, the metal salt, the anode material, the conductive agent and the binder are mixed and dispersed in an organic solvent, and then the mixture is coated on an aluminum foil, irradiated by ultraviolet light and dried to obtain the anode layer 200.
The negative electrode layer 400 comprises a negative electrode material, a conductive agent, a binder and a polymer solid electrolyte, wherein the content of the negative electrode material, the content of the conductive agent, the content of the binder and the content of the polymer solid electrolyte in the negative electrode layer 400 are respectively 50-99.8%, 0.1-15%, 0-5% and 0.1-30% by mass fraction. Optionally, the main material of the negative electrode material is one or more of lithium powder, graphite, silicon carbon and SiOx, and the particle diameter of the main material is 0.01-50 μm. Optionally, the binder is one or more of styrene butadiene rubber, polyacrylate and polyacrylate, and the weight average molecular weight of the binder is 1 to 500 ten thousand. The negative electrode layer 400 in this embodiment may be manufactured by the following method: the grafted silicon dioxide, the monomer 1, the monomer 2, the metal salt, the negative electrode material, the conductive agent and the binder are mixed and dispersed in an organic solvent, and then the mixture is coated on a copper foil, irradiated by ultraviolet light and dried to obtain the negative electrode layer 400. Of course, in some other embodiments, the negative electrode layer 400 may also be a lithium metal foil or a lithium copper composite foil, which is not described herein again.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides an all-solid-state battery, and a preparation method thereof is as follows:
s100, preparing the positive plate.
0.163g of monomer 1, 0.537g of monomer 2, and 0.2g of LiBF were sampled 4 0.1g of grafted silicon dioxide, 20mL of N-methylpyrrolidone are added to disperse the silicon dioxide uniformly, and 8g of lithium cobaltate serving as a positive electrode active substance and 0.5g of ethyl acetate serving as a conductive agent are addedUniformly dispersing acetylene black (the particle diameter is 10nm) and 0.5g of polyvinylidene fluoride serving as a binder, finally coating the dispersed slurry on a 12-micron aluminum current collector, irradiating the aluminum current collector for 2 hours by using ultraviolet light, drying the aluminum current collector at 80 ℃, and controlling the production process parameters to obtain the positive plate with the thickness of 40 microns.
Wherein the monomer 1 is:
monomer 2 is
Cation(s)
Is a lithium ion. The preparation method of the grafted silicon dioxide comprises the following steps:
modifying the nano-scale silicon dioxide subjected to ultrasonic treatment by using a silane coupling agent to obtain grafted silicon dioxide, wherein the silane coupling agent is
And S200, preparing a negative plate.
0.163g of monomer 1, 0.537g of monomer 2, and 0.2g of LiBF were sampled 4 0.1g of grafted silica, dispersed in 20mL of chloroform-toluene (the volume ratio of chloroform to toluene is 1: 1), and then graphite as a negative electrode active material, carbon nanotubes as a conductive agent, and Styrene Butadiene Rubber (SBR) as a binder were added and uniformly dispersed. Wherein the mass of the graphite, the carbon nano tube and the SBR are respectively 8g, 0.5g and 0.5 g. And finally, coating the dispersed slurry on a 10-micron copper current collector, irradiating the copper current collector for 2 hours by using ultraviolet light, and drying the copper current collector at 80 ℃ to obtain a negative plate with the thickness of 45 microns.
And S300, preparing a polymer solid electrolyte layer.
1.63g of monomer 1, 5.37g of monomer 2, 2g of LiBF were added 4 1g of the grafted silica was mixed and dispersed in 200mL of tetrahydrofuran, and then the above mixture was cast on a PET film while irradiating with ultraviolet light for 2 hours to polymerize the grafted silica, monomer 1, monomer 2Forming polymer electrolyte, and drying and stripping to obtain the corresponding polymer solid electrolyte layer with the thickness of 20 μm.
S400, preparing the all-solid-state lithium battery
And assembling the prepared polymer electrolyte layer, the positive plate and the negative plate in a lamination mode, and performing hot pressing at 100 ℃ to obtain the all-solid-state lithium battery with the structure shown in figure 3.
Example 2
The embodiment provides an all-solid-state battery, and a preparation method thereof is as follows:
s100, preparing the positive plate.
Taking 0.138g of monomer 1, 0.562g of monomer 2 and 0.2g of LiPF 6 0.1g of grafted silicon dioxide, 20mL of N-methyl pyrrolidone is added to uniformly disperse the silicon dioxide, 8g of lithium cobaltate as a positive electrode active material, 0.5g of acetylene black (the particle diameter is 10nm) as a conductive agent and 0.5g of polyvinylidene fluoride as a binding agent are added to uniformly disperse the silicon dioxide, and finally the dispersed slurry is coated on a 12 mu m aluminum current collector and is irradiated by ultraviolet light for 2 hours, and after drying at 80 ℃, the production process parameters are controlled to obtain a positive electrode plate with the thickness of 40 mu m.
Wherein the monomer 1 is
Monomer 2 is
Cation(s)
Is magnesium ion; the preparation method of the grafted silicon dioxide comprises the following steps:
modifying the nano-scale silicon dioxide subjected to ultrasonic treatment by using a silane coupling agent to obtain grafted silicon dioxide, wherein the silane coupling agent is
And S200, preparing a negative plate.
Taking 0.138g of monomer 1, 0.562g of monomer 2 and 0.2g of LiPF 6 0.1g of grafted silica, dispersed in 20mL of chloroform-toluene (the volume ratio of chloroform to toluene is 1: 1), and then graphite as a negative electrode active material, carbon nanotubes as a conductive agent, and Styrene Butadiene Rubber (SBR) as a binder were added and uniformly dispersed. Wherein the mass of the graphite, the carbon nano tube and the SBR is 8g, 0.5g and 0.5g respectively. And finally, coating the dispersed slurry on a 10-micron copper current collector, irradiating the copper current collector for 2 hours by using ultraviolet light, and drying the copper current collector at 80 ℃ to obtain a negative plate with the thickness of 45 microns.
And S300, preparing a polymer solid electrolyte layer.
1.38g of monomer 1, 5.62g of monomer 2, 2g of LiPF 6 1g of grafted silica is mixed and dispersed in 200mL of tetrahydrofuran, then the mixture is cast on a PET film and simultaneously irradiated by ultraviolet light for 2 hours to ensure that the grafted silica, the monomer 1 and the monomer 2 are polymerized to form a polymer electrolyte, and then the polymer electrolyte is dried and stripped to obtain a corresponding polymer solid electrolyte layer, wherein the thickness of the obtained polymer solid electrolyte layer is 20 microns.
S400, preparing the all-solid-state lithium battery
And assembling the prepared polymer electrolyte layer, the positive plate and the negative plate in a lamination mode, and carrying out hot pressing at 100 ℃ to obtain the all-solid-state lithium battery with the structure shown in figure 3.
Example 3
The embodiment provides an all-solid-state battery, and a preparation method thereof is as follows:
s100, preparing the positive plate.
Taking 0.271g of monomer 1, 0.429g of monomer 2, 0.2g of LiTFSI and 0.1g of grafted silicon dioxide, adding 20mL of N-methylpyrrolidone to uniformly disperse the N-methylpyrrolidone, then adding 8g of lithium cobaltate serving as a positive electrode active material, 0.5g of acetylene black (the particle diameter is 10nm) serving as a conductive agent and 0.5g of polyvinylidene fluoride serving as a binding agent to uniformly disperse the N-methylpyrrolidone, finally coating the dispersed slurry on a 12 mu m aluminum current collector, irradiating the aluminum current collector with ultraviolet light for 2 hours, drying the aluminum current collector at 80 ℃, and controlling the production process parameters to obtain a positive electrode plate with the thickness of 40 mu m.
Wherein the monomer 1 is
Monomer 2 is
Cation(s)
Is composed of
R 1 、R 2 、R 3 、R 4 Are all n-propyl; the preparation method of the grafted silicon dioxide comprises the following steps:
modifying the nano-scale silicon dioxide subjected to ultrasonic treatment by using a silane coupling agent to obtain grafted silicon dioxide, wherein the silane coupling agent is
And S200, preparing a negative plate.
0.271g of the monomer 1, 0.429g of the monomer 2, 0.2g of LiTFSI, 0.1g of grafted silica were dispersed in 20mL of chloroform-toluene (the volume ratio of chloroform to toluene was 1: 1), and then graphite as a negative electrode active material, carbon nanotubes as a conductive agent, and Styrene Butadiene Rubber (SBR) as a binder were added and uniformly dispersed. Wherein the mass of the graphite, the carbon nano tube and the SBR are respectively 8g, 0.5g and 0.5 g. And finally, coating the dispersed slurry on a 10-micron copper current collector, irradiating the copper current collector for 2 hours by using ultraviolet light, and drying the copper current collector at 80 ℃ to obtain a negative plate with the thickness of 45 microns.
And S300, preparing a polymer solid electrolyte layer.
2.71g of monomer 1, 4.29g of monomer 2, 2g of LiTFSI and 1g of grafted silica are mixed and dispersed in 200mL of tetrahydrofuran, then the mixture is cast on a PET film and simultaneously irradiated by ultraviolet light for 2 hours to polymerize the grafted silica, the monomer 1 and the monomer 2 to form a polymer electrolyte, and then drying and stripping are carried out to obtain a corresponding polymer solid electrolyte layer, wherein the thickness of the obtained polymer solid electrolyte layer is 20 micrometers.
S400, preparing the all-solid-state lithium battery
And assembling the prepared polymer electrolyte layer, the positive plate and the negative plate in a lamination mode, and carrying out hot pressing at 100 ℃ to obtain the all-solid-state lithium battery with the structure shown in figure 3.
Example 4
The embodiment provides an all-solid-state battery, and a preparation method thereof is as follows:
s100, preparing the positive plate.
Taking 0.317g of monomer 1, 0.383g of monomer 2, 0.2g of LiFSI and 0.1g of grafted silicon dioxide, adding 20mL of N-methylpyrrolidone to uniformly disperse the N-methylpyrrolidone, then adding 8g of lithium cobaltate serving as an anode active substance, 0.5g of acetylene black (the particle diameter is 10nm) serving as a conductive agent and 0.5g of polyvinylidene fluoride serving as a binder to uniformly disperse the N-methylpyrrolidone, finally coating the dispersed slurry on a 12 mu m aluminum current collector, irradiating the aluminum current collector with ultraviolet light for 2 hours, drying the aluminum current collector at 80 ℃, and controlling production process parameters to obtain an anode plate with the thickness of 40 mu m.
Wherein the monomer 1 is
Monomer 2 is
Cation(s)
Is composed of
R 1 、R 2 、R 3 、R 4 Are all ethyl; the preparation method of the grafted silicon dioxide comprises the following steps:
modifying the nano-scale silicon dioxide subjected to ultrasonic treatment by using a silane coupling agent to obtain grafted silicon dioxide, wherein the silane coupling agent is
And S200, preparing a negative plate.
0.317g of the monomer 1, 0.383g of the monomer 2, 0.2g of LiFSI and 0.1g of grafted silica were dispersed in 20mL of chloroform-toluene (the volume ratio of chloroform to toluene was 1: 1), and then graphite as a negative electrode active material, carbon nanotubes as a conductive agent and Styrene Butadiene Rubber (SBR) as a binder were added and uniformly dispersed. Wherein the mass of the graphite, the carbon nano tube and the SBR are respectively 8g, 0.5g and 0.5 g. And finally, coating the dispersed slurry on a 10-micron copper current collector, irradiating the copper current collector for 2 hours by using ultraviolet light, and drying the copper current collector at 80 ℃ to obtain a negative plate with the thickness of 45 microns.
And S300, preparing a polymer solid electrolyte layer.
3.17g of monomer 1, 3.83g of monomer 2, 2g of LiFSI and 1g of grafted silicon dioxide are mixed and dispersed in 200mL of tetrahydrofuran, then the mixture is cast on a PET film, ultraviolet light is used for irradiating for 2 hours simultaneously to polymerize the grafted silicon dioxide, the monomer 1 and the monomer 2 to form a polymer electrolyte, and then drying and stripping are carried out to obtain a corresponding polymer solid electrolyte layer, wherein the thickness of the obtained polymer solid electrolyte layer is 20 microns.
S400, preparing the all-solid-state lithium battery
And assembling the prepared polymer electrolyte layer, the positive plate and the negative plate in a lamination mode, and carrying out hot pressing at 100 ℃ to obtain the all-solid-state lithium battery with the structure shown in figure 3.
Comparative example 1
The present comparative example provides an all-solid battery, the preparation method of which is as follows:
s100, preparing the positive plate.
0.8g of polyethylene oxide (PEO for short, molecular weight 6X 10) 5 g/mol) and 0.2g LiTFSI into 20mL of N-methylpyrrolidone for dissolving, then adding 8g of lithium cobaltate as an anode active material, 0.5g of acetylene black as an auxiliary agent and 0.5g of polyvinylidene fluoride as a binder for uniformly dispersing, finally coating the dispersed slurry on a 12 mu m aluminum current collector, drying at 80 ℃, and obtaining an anode plate with the thickness of 40 mu m by controlling production process parameters.
And S200, preparing a negative plate.
0.8g of PEO and 0.2g of LiTFSI were dissolved in 20mL of chloroform-toluene (the volume ratio of chloroform to toluene was 1: 1), and then graphite as a negative electrode active material, carbon nanotubes as a binder and a conductive agent, and SBR as a binder were added and uniformly dispersed. Wherein the mass of the graphite, the carbon nano tube and the SBR are respectively 8g, 0.5g and 0.5 g. And finally, coating the dispersed slurry on a 10-micron copper current collector, and drying at 80 ℃ by controlling production process parameters to obtain a 45-micron negative plate.
S300, preparing a polymer electrolyte layer.
8g of polyethylene oxide and 2g of LiTFSI are dissolved in 200mL of acetonitrile to form a polymer electrolyte, finally, the dissolved solution is cast on a PET film by using a casting method, the PET film is dried and peeled to form a film, and a PEO-containing polymer electrolyte layer with the thickness of 30 mu m is prepared by controlling the parameters of a synthesis process.
And S400, preparing the all-solid-state lithium battery.
And (3) slicing the prepared polymer electrolyte, the anode and the cathode, assembling in a lamination mode, and carrying out hot pressing at 100 ℃ to obtain the all-solid-state lithium battery.
Comparative example 2
This comparative example provides an all-solid battery whose preparation method differs from that of example 1 mainly as follows:
in each of S100, S200 and S300, 1, 4-divinylbenzene was used in place of the monomer 2.
Comparative example 3
This comparative example provides an all-solid battery whose preparation method differs from that of example 1 mainly as follows:
s100, S200 and S300 do not contain grafted silicon dioxide; in S100 and S200, the monomer 1, the monomer 2 and the LiBF are 4 The mass of the powder is 0.186g, 0.614g and 0.2g respectively; in S300, monomer 1, monomer 2 and LiBF 4 The mass of (A) was 1.86g, 6.14g and 2g, respectively.
Application example
Polymer solid electrolyte Performance testing
Tensile strengths of the polymer solid electrolytes in examples and comparative examples were measured as follows: a polymer solid electrolyte membrane having a thickness of 100 μm was sampled with a sampler to obtain a sample having a length of 10cm and a width of 1.5 cm. The sample was then subjected to a tensile test in a tensile tester at a running speed of 10 mm/min. And recording the maximum tensile strength value after the test is stopped.
For the ionic conductivity measurements in the examples and comparative examples, the measurements were made as follows: taking the polymer electrolyte, and combining the polymer electrolyte with a stainless steel sheet respectively to manufacture a CR2025 type button cell; the obtained cell was put in a jig at a constant temperature of 25 ℃ for 5 hours, and an electrochemical impedance test was carried out in a frequency range of 1Hz to 8MHz, after which the ionic conductivity of the polymer solid electrolyte was calculated based on the measured electrolyte impedance and the following formula:
σ＝h/RS；
wherein σ is the ionic conductivity of the electrolyte and has a unit of S-cm -1 (ii) a h is the thickness of the electrolyte membrane in cm; r is the bulk impedance of the polymer electrolyte measured by electrochemical impedance method, and has a unit of Ω (or S) -1 ) (ii) a S is the contact area of the electrolyte and the stainless steel sheet, and the unit is cm 2 。
The results of the performance test of the polymer solid electrolytes of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 tensile strength and ionic conductivity of Polymer solid electrolyte
From this, it is understood that the polymer solid electrolyte in the present example has good mechanical strength and conductivity, compared to the comparative example.
Solid state battery performance testing
The charge and discharge performance of the all-solid-state batteries obtained in examples 1 to 4 and comparative examples 1 to 3 was tested, and the test procedure was as follows:
each all-solid-state battery was thermostatted at various temperatures (-50 ℃, 25 ℃, 100 ℃ and 200 ℃) for 5 hours. Thereafter, the cell was charged at a constant current of 3.0V to 4.2V at a rate of 0.5C, left to stand for 5 minutes, then charged at a constant voltage of 4.2V to 0.05C, and finally discharged at a rate of 0.5C to 3.0V, and left to stand for 5 minutes. At different temperatures, the discharge specific capacities of all-solid-state batteries are as follows:
TABLE 2 discharge behavior of all-solid-state batteries at different temperatures
All the solid-state batteries prepared above are kept at constant temperature for 5 hours at different temperatures (-50 ℃, 25 ℃, 100 ℃ and 200 ℃). Then, constant current charging from 3.0V to 4.2V at a rate of 0.5C, then standing for 5 minutes, then constant voltage charging to 0.05V at 4.2V to cut off, discharging to 3.0V at a rate of 0.5C, and finally standing for 5 minutes, and repeating the above steps for 100 times to obtain the cycle performance as follows:
TABLE 3 cycling performance of all-solid-state batteries at different temperatures
In tables 2 and 3, "-" in the tables represents that the data could not be measured because the all-solid battery in comparative example 1 was short-circuited at temperatures such as 100 c and 200 c, which indicates that the all-solid battery in comparative example 1 was not resistant to high temperature.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (12)
1. A method of preparing a polymer solid electrolyte, comprising the steps of:
mixing grafted silica, a monomer 1, a monomer 2 and a metal salt in an organic solvent, and then catalyzing to polymerize the grafted silica, the monomer 1 and the monomer 2;
the structural general formula of the monomer 1 is as follows:
wherein i is any value between 0 and 500; the structural general formula of the monomer 2 is as follows:
wherein j is an arbitrary value between 0 and 10, k is an arbitrary value between 0 and 10, and cation Y ⊕ Is at least one of alkali metal ions, alkaline earth metal ions and structures shown in formulas 1 to 7; wherein the formula 1:
formula 2:
formula 3:
formula 4:
formula 5:
formula 6:
formula 7:
R 1 、R 2 、R 3 、R 4 are each hydrogen or carbonAn alkyl group having 1 to 10 atoms.
2. The method for producing a polymer solid electrolyte according to claim 1, wherein polymerization occurs between the grafted silica, the monomer 1, and the monomer 2 by photocatalysis.
3. The method for producing a polymer solid electrolyte according to claim 1, wherein the metal salt is a lithium salt.
4. The method for producing a polymer solid electrolyte according to claim 3, wherein the lithium salt comprises LiP (R) f1 R f2 R f3 R f4 R f5 R f6 )、LiB(R f1 R f2 R f3 R f4 )、LiN(SO 2 R f1 )(SO 2 R f2 )、LiC(SO 2 R f1 )(SO 2 R f2 )(SO 2 R f3 ) At least one of lithium difluoro oxalate borate, lithium bis (oxalate) borate, lithium perchlorate and lithium hexafluoroarsenate, wherein R is f1 、R f2 、R f3 、R f4 、R f5 、R f6 Are respectively C n F 2n+1 Wherein n is more than or equal to 0 and less than or equal to 10; optionally, the lithium salt is LiPF 6 、LiBF 4 、LiTFSI、LiFSI、LiDFOB、LiBOB、LiClO 4 、LiAsF 6 At least one of (1).
5. The method for producing a polymer solid electrolyte according to claim 1, wherein the grafted silica is 0.5 to 50% by mass, the monomer 1 is 0.25 to 25% by mass, the monomer 2 is 0.25 to 25% by mass, and the metal salt is 0 to 99% by mass.
6. The method for producing a polymer solid electrolyte according to claim 1, wherein the grafted silica is a silica obtained by modifying a silica with a silane coupling agent
7. A polymer solid electrolyte prepared by the method according to any one of claims 1 to 6.
8. A solid-state battery comprising an aluminum current collector, a positive electrode layer, a polymer solid-state electrolyte layer, a negative electrode layer, and a copper current collector, which are stacked in this order, wherein the polymer solid-state electrolyte layer is formed of the polymer solid-state electrolyte according to claim 7.
9. The solid-state battery according to claim 8, wherein the thickness of the copper current collector is 10nm to 20 μm; and/or the thickness of the aluminum current collector is 10 nm-20 μm; and/or the thickness of the anode layer is 10 nm-100 μm; and/or the thickness of the negative electrode layer is 10 nm-100 mu m; and/or the thickness of the polymer solid electrolyte layer is 10 nm-100 mu m.
10. The solid-state battery according to claim 8, wherein the positive electrode layer includes a positive electrode material, a conductive agent, a binder, the polymer solid-state electrolyte;
optionally, the content of the positive electrode material is 50-99.8%, the content of the conductive agent is 0.1-15%, the content of the binder is 0-5%, and the content of the polymer solid electrolyte is 0.1-30% by mass;
optionally, the positive electrode material is carbon-coated LiM 1 PO 4 And/or LiM 2 O 2 Wherein the element M 1 Is one or more elements of Fe, Co, Ni and Mn, and element M 2 The anode material is one or more of Ni, Co, Mn and Al, and the particle diameter of the anode material is 0.01-50 mu m;
optionally, the conductive agent is one or more of carbon black, acetylene black and carbon nanotubes, and the particle diameter of the conductive agent is 0.01-50 μm;
optionally, the binder is one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), polytetrafluoroethylene, polyacrylate and polyacrylate, and the weight average molecular weight of the binder is 1 to 500 ten thousand.
11. The solid-state battery according to claim 8, wherein the negative electrode layer includes a negative electrode material, a conductive agent, a binder, the polymer solid-state electrolyte;
optionally, the content of the negative electrode material is 50-99.8%, the content of the conductive agent is 0.1-15%, the content of the binder is 0-5%, and the content of the polymer solid electrolyte is 0.1-30% by mass;
optionally, the negative electrode material is one or more of lithium powder, graphite, silicon carbon and SiOx, and the particle diameter of the negative electrode material is 0.01-50 μm;
optionally, the conductive agent is one or more of carbon black, acetylene black and carbon nanotubes, and the particle diameter of the conductive agent is 0.01-50 μm;
optionally, the binder is one or more of styrene butadiene rubber, polyacrylate and polyacrylate, and the weight average molecular weight of the binder is 1 to 500 ten thousand.
12. The solid-state battery according to claim 8, wherein the negative electrode layer is a lithium metal foil or a lithium copper composite foil.
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